Concepts For The Incorporation of Inorganic Building Blocks Into Organic Polymers On A Nanoscale

Prog. Polym. Sci.
28 (2003) 83114
www.elsevier.com/locate/ppolysci
Concepts for the incorporation of inorganic building blocks

into organic polymers on a nanoscale
Guido Kickelbick*
Institut fur Materialchemie, Technische Universitat Wien, Getreidemarkt 9, A-1060 Wien, Austria
Received 13 November 2001; revised 25 February 2002; accepted 15 March 2002
Abstract
Hybrid inorganic organic materials are promising systems for a variety of applications due to their extraordinary
properties based on the combination of the different building blocks. The combination of nanoscale inorganic moieties
with organic polymers has a high potential for future applications and has therefore attracted a lot of attention during the
last years. Since there are countless different combinations of the two moieties, there are also a large number of
methodologies to combine them in one material. This review is written with the intention to give an overview of
principal concepts of the preparation of such materials for different applications. It focuses on the chemical aspects of the
incorporation of inorganic building blocks such as silica networks, porous materials, metals, etc. into an organic
polymeric matrix. q 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Hybrid materials; Nanocomposites; Polymers; Nanoparticles
Contents
1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2. Interpenetrating networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.1. Sol gel process in presence of preformed polymer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.2. Polymerization in sol gel networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.3. Simultaneous formation of interpenetrating networks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
2.4. Dual network precursors. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3. Incorporation of metals and metal complexes in polymers by coordination interactions . . . . . . . . . . . .
3.1. Coordination of metals to the polymer backbone . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.2. Metal-coordinated monomers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
3.3. Metal-centered polymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
4. Intercalation in 2D layered materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
5. Intercalation in 3D frameworks: zeolites, molecular sieves and M41S-materials . . . . . . . . . . . . . . . . .
6. Incorporation of inorganic particles and clusters. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.1. Incorporation of unmodified particles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.2. Encapsulation of particles in a polymer shell . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.3. In situ growth of inorganic particles in a polymer matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.4. Surface-modification with polymerizable groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
6.5. Surface-modification with initiating groups . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
7. Nanoengineering of composite materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
8. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
9. Summary . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .
* Tel.: 43-1-58801-15321; fax: 43-1-58801-15399.

E-mail address: kickelgu@mail.zserv.tuwien.ac.at (G. Kickelbick).
0079-6700/03/$ - see front matter q 2002 Elsevier Science Ltd. All rights reserved.
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G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
1. Introduction
Inorganic organic composite materials are increasingly
important due to their extraordinary properties, which arise
from the synergism between the properties of the components. There are several routes to these materials, but
probably the most prominent one is the incorporation of
inorganic building blocks in organic polymers. These
materials have gained much interest due to the remarkable
change in properties such as mechanical [1], thermal [2 5],
electrical [6], and magnetic [7] compared to pure organic
polymers. The most commonly employed preparation
procedures for these materials are the use of the sol gel
process for the formation of the inorganic network, the
incorporation of preformed dense inorganic structures, such
as clusters and particles, and the formation of hybrids using
porous or layered inorganic materials either by interpenetration of the organic polymers into the voids, or by
exfoliation of the inorganic material. The unique properties
of these materials, such as their high optical transparency, as
well as the lack of data on structure property relationships
at a nanoscale, has led to emerging research in this area.
Most of the efforts are based on well-known macro- or
microcomposites between inorganic moieties and organic
polymers, and expand ideas from this microcosmos to a new
class of materials, called nanocomposites [8]. Expressions
like nanoparticles and nanocomposites seem to be very
trendy, and are often misused in the literature for systems
which do not properly fall under the label nano in the sense
of advertising. Aside from the inappropriate use of the term
nano, there is a strong need to understand the mechanism of
the formation of such materials. Important aspects of the
chemistry involved in the formation of these systems are the
uniformity, phase continuity, domain sizes and the molecular mixing at the phase boundaries, which all have a direct
influence on optical, physical, and mechanical properties
[9]. Owing to numerous papers published on polymer
organic inorganic composite materials, it is impossible to
completely review this field. Therefore, this review will
focus on the most common principal concepts used to
incorporate inorganic systems in the submicron range (up to
a few hundreds of nanometers) into an organic polymeric
matrix, and the resulting properties of such materials. The
reader is referred to the literature cited for a more detailed
description.
While the incorporation of microscale and larger
inorganic fillers into organic polymers is scientifically
well explored, the decrease in size of the inorganic
component into the nano dimension, and the simultaneous
increase of the interfacial area, results in new extraordinary
materials properties which require further investigations.
Additionally, the properties of the composite materials

depend on the morphology of the phases, which has to be
controlled over several length scales. Therefore, the
development of such materials is a land of multidisciplinarity [10], where chemists, physicists, material scientists
and engineers have to work closely together.
From a chemical point of view, one can distinguish
between several ways to incorporate inorganic systems in
organic polymers depending on the interactions between the
moieties: materials with strong (covalent, coordination,
ionic): weak (van-der-Waals, hydrogen-bonds, hydrophilic hydrophobic balance); or without chemical interactions
between the two components (Fig. 1) [10,11]. A critical
challenge in the design of these hybrid inorganic organic
systems is a control of the mixing between the two
dissimilar phases. Several chemical approaches that may
be applied to overcome this problem will be described in
this review.
2. Interpenetrating networks
The formation of interpenetrating networks (IPNs)
between inorganic and organic moieties is carried out either
by a sequential two-step process, wherein a secondary
network is formed in a primary one, or by the simultaneous
formation of the two networks. The resulting materials are
microscopically phase separated, but macroscopically
uniform [12]. Examples of the two-step process include
the creation of an organic polymer penetrating into the pores
of an inorganic porous material, such as a zeolite or
mesoporous amorphous materials, or between the sheets of a
layered lattice, such as a clay mineral. In these cases the
inorganic moiety is a rigid, preformed natural or synthetic
host matrix, with a regular pore or channel structure in the
nanoscale. In another process, an inorganic (crosslinked)
moiety is formed by a polycondensation reaction, and
interpenetrates during this process into an organic polymer.
Difficulties of such an approach are potential incompatibilities between the moieties, leading to phase separation,
and the challenge to find reactions for the formation of the
second network which can be carried out in the presence of
the first one. A major problem arises from the different
stabilities of the materials. While inorganic systems are
thermally quite stable and are often formed at high
temperature, most organic polymers have an upper temperature limit of around 250 8C. Therefore, the synthesis of
hybrid systems requires a strategy wherein the formation of
the components is well-suited to each, e.g. the use of a lowtemperature formation procedure. Hence, classical high
temperature solid-state reactions for the preparation of the
Nomenclature
AA
An
ATRP
BA
bpy
DMAA
DMA
DSC
EA
EO
GLYMO
HEA
HEMA
IPN
MA
MAc
MEMO
MMA
2MOx
NVP
PDMS
PTA
PV
Py
SANS
SAXS
SEM
St
TEOS
TEM
TFEA
TMO
TMOS
Tp
VA
VAc
VE
2VP
4VP
4VPh
acrylamide
aniline
atom transfer radical polymerization
n-butyl acrylate
2,20 -bipyridine
N,N-dimethylacrylamide
dynamic mechanical analysis
differential scanning calorimetry
ethyl acrylate
ethylene oxide
3-glycidoxypropyltrimethoxysilane
2-hydroxyethyl acrylate
2-hydroxyethyl methacrylate
interpenetrating network
methyl acrylate
methacrylic acid
3-methacryloxypropyltrimethoxysilane
methyl methacrylate
2-methyl-2-oxazoline
N-vinylpyrrolidone
polydimethylsiloxane
phenyleneterephthalamide
p-phenylenevinylene
pyrrole
small angle neutron scattering
small angle X-ray scattering
scanning electron microscopy
styrene
tetraethoxysilane
transmission electron microscopy
2,2,2-trifluoroethyl acrylate
tetramethylene oxide
tetramethoxysilane
thiophene
vinyl alcohol
vinylacetate
vinylether
2-vinylpyridine
4-vinylpyridine
4-vinylphenol
inorganic component must fail due to the limited thermal

stability of the organic polymers. For this reason milder
reactions have to be applied for the formation of the
inorganic network. An ideal procedure for the generation of
such hybrid materials is the sol gel process [13]. This
process starts with molecular precursors at ambient
temperatures, forming metal oxide frameworks by hydrolysis and condensation reactions (Scheme 1). The morphologies and properties of the resulting materials are
controlled by the reaction conditions and the precursors
used. Typical sol gel processing variables leading to
85
different morphologies of the materials are the water to

alkoxy and catalyst to alkoxy ratios, and the type of solvent
and catalyst used. For example, whereas optically transparent silicate/polymer hybrid materials are often obtained in
an acid catalyzed sol gel process, nucleophilic catalysts
such as fluorides or hydroxides give opaque materials due to
a more particulate inorganic phase [14]. The most prominent
inorganic material formed by the sol gel method is
unmodified or modified SiO2, using precursors of the type
Si(OR)4 for unmodified networks or R0n SiOR42n for
modified networks. Contrary to other metal alkoxides, the
C Si bond is stable with respect to hydrolysis, and therefore
a variety of modifications can be directly and durably
incorporated into the SiO2 network. The organic groups
introduced into the sol gel precursor can fulfill two
functions: (i) modification of the inorganic network,
resulting in improved compatibility between the two phases,
and/or (ii) the formation of a strong linkage between the
organic and the inorganic phase via covalent bonds.
Furthermore, the process may be extended to metal oxide
networks using various metal alkoxide precursors [15].
Although silicon alkoxides are probably most studied, other
metals often used include tin, titanium, zirconium, cerium,
and aluminum. As the M C bond is not hydrolytically
stable, the incorporation of functional groups requires
another methodology, for example, via the coordination of
multidentate functional ligands, which show a higher
stability towards substitution reactions. Frequently used
strategies for the formation of IPN hybrid materials applying
the sol gel approach are: (i) mixing of the precursor for the
sol gel process with the organic polymer followed by an
inorganic polycondensation reaction, (ii) polymerization of
an organic monomer in the inorganic gel, (iii) simultaneous
formation of the inorganic and organic network, and (iv)
dual network materials in which the molecular precursors
for the formation of the two networks are covalently linked
to each other (telechelics, etc.). The amount of incorporated
inorganic moiety can be varied over a wide range. In
addition to the sol gel processing parameters, the morphology of the hybrid materials obtained by the interpenetration of polymers and inorganic moieties is dependent on
polymer variables such as the molecular weight, the
presence and extent of polymer functionality and shape,
and the solubility of the polymer in the sol solution.
Therefore, possibilities for synthesizing this type of
material are immense, and only a small selection can be
presented here.
2.1. Sol gel process in presence of preformed polymer
A typical application area for hybrid materials are optical
systems that require homogeneous and transparent materials
which cannot be obtained from mixtures that are already
macroscopically phase separated. This is often the case if
hydrophobic polymers are mixed with sol gel solutions.
Therefore, organic polymers with functional groups that
86
Fig. 1. Different kinds of inorganic organic composite materials. (a) embedding of the inorganic moiety into the organic polymer, (b)
interpenetrating networks (IPNs); with chemical bonds: (c) incorporation of inorganic groups by bonding to the polymer backbone, and (d) dual
inorganicorganic hybrid polymer.
have specific interactions with compounds created in the

sol gel process, e.g. hydrogen bonding to residual silanol
groups on the formed silica, have to be chosen. A broad
variety of organic polymers with hydrogen bonding ability
such as poly(2MOx), poly(VP), poly(DMAA), poly(VA),
poly(MMA), poly(VAc), polyamides, polyethersulfones
[16], polymeric perfluoroalkylsulfonates (Nafion) [17 20],
and hydroxy end-capped polysiloxanes were incorporated
into sol gel reaction mixtures [21 28]. Due to the
interactions between the polymer and the silanol groups
generated during the sol gel process, a macrophase
separation is avoided, and the resulting materials have a
high degree of homogeneity and optical transparency.

However, this property is dependent on the reaction
conditions of the sol gel process, e.g. the pH value. Similar
interactions are observed when poly(oxypropylene) is used
in the formation of epoxide amine networks reinforced by
SiO2. The resulting materials show strong structural
differences depending on whether a one step or a two-step
procedure was used to form the IPNs [29 31].
While in most of the studies, tetraalkoxysilanes were
used as precursors for the inorganic network, trialkoxysilanes with an organic functionality have also been
employed. Often the organic group has a significant
Scheme 1.
influence on the resulting material. In a hybrid material

formed from poly(VAc) and phenyltriethoxysilane it was
observed that the glass transition temperature (Tg) of the
polymer increases in a similar way as it does with TEOS as
precursor. However, a mechanical reinforcement of the
polymer has not been observed [32]. This behavior probably
has its origin in the different extend of network formation
with the two silicate precursors. In the case of tetraalkoxysilane, depending on the reaction conditions, a highly
crosslinked silica network can be formed, while in the case
of trialkoxysilanes a lower degree of crosslinking is usually
observed. Additionally, the functionality of the trialkoxysilane can be used for the formation of a covalent linkage
between the polymer and the silica species. For example,
aminophenyltrimethoxysilane was used as a compatibilizer
which reacts with the phthaloyl chloride end-capped
polyamide [27,33]. In another study, the interfacial bonding
between the phases of hydroxypolybenzoxazole and sulfopolybenzobisthiazole polymers and the silica, is improved
by the use of isocyanatopropyltriethoxysilane and N,Ndiethylaminopropyltrimethoxysilane, respectively [34].
Inorganic polymers such as polyphosphazenes modified
with methoxyethoxyethoxy side groups also show hydrogen
bonding to the silicate species. Optically transparent
composite films with titania, zirconia and alumina were
formed with these inorganic polymers as well as with purely
organic macromolecules [35,36].
If the time of the sol gel network formation is fast
enough, a macroscopic phase separation is avoided. This
was proved applying the very fast non-aqueous sol gel
process where formic acid is used together with silicon
alkoxides. In this process the water necessary for the
condensation of the silicate species is produced by an
esterification reaction of the alcohols released by the silica
precursor and formic acid. In these systems, a TEOS/
poly(MMA) hybrid can be obtained in 15 min compared to
200 h using the usually employed systems [37]. Another
way to enhance the homogeneity of the hybrid materials is
the use of polymeric compatibilizers such as copolymers of
poly(St) and poly(4VPh) which help to reduce the interfacial
tension in incompatible systems [38]. Applying this method
the particle size of the silicate species can be significantly
reduced leading to a better adhesion between the organic
polymer and the inorganic moieties.
The sol gel process can be employed using a variety of
different inorganic precursors, therefore the inorganic part
of the hybrid material is not limited to SiO2. Examples are
composites of poly(BA), PDMS or poly(PTA) with
titania/silica or pure titania species [39 43]. Composite
materials with inorganic species such as zirconia or mixed
silica titania or silica alumina have been produced using
Nafion as the polymer component [44,45].
It is important to mention that the parameters employed
for the sol gel process have a crucial influence on the
morphology of the inorganic species in the resulting
material which directly influences its properties [46].
87
2.2. Polymerization in sol gel networks

Similar to the mixing of preformed organic polymers with
the precursors for the solgel process, a mixing between silica
and the monomers of an organic polymer is problematic if no
attracting interactions between the two phases exist.
The high porosity of a silica network formed by the sol
gel process can be used for an impregnation of the material
with polymers as well as with monomers, which can be
polymerized in situ. With such a technique, poly(MMA)/
silica hybrids were prepared, and it was shown that the
mechanical properties of the pure silica species can be
improved significantly depending on the amount of poly
(MMA) included and by the addition of a coupling agent
such as methacryloxytrimethoxysilane [47].
Swelling of sol gel derived crosslinked poly(TMO)
silica hybrids in various monomers such as cyclohexyl
methacrylate, VP or Mac, and polymerization with 60Co
gamma radiation resulted in transparent hydrogels. These
materials revealed significant changes in the mechanical and
dynamic mechanical properties, such as the elastic modulus,
which increased in some cases by several magnitudes,
compared to the precursor systems [48,49].
Contrary to the polymerization in sol gel networks, the
infiltration of preformed polymers into these networks is
rare due to the difficulties connected with the slow diffusion
of organic polymer chains into the porous inorganic network
structure. As a result the infiltration of the monomer and an
in situ polymerization is preferred.
2.3. Simultaneous formation of interpenetrating networks
The simultaneous formation of two networks can result in
the most homogeneous type of materials. Applying this
method towards hybrid materials three processes are in
competition: (i) the kinetics of the hydrolysis and condensation
forming the inorganic phase, (ii) the kinetics of the
polymerization of the organic phase, and (iii) the thermodynamics of the phase separation between the two phases. If the
kinetics of the two network-forming processes are tailored in
such a way that they occur simultaneously and rapidly enough,
phase separation can be avoided or minimized, thus producing
a homogeneous material. Additional parameters such as
attractive interactions between surface hydroxy groups of
the solgel products and the organic monomer, for instance,
hydrogen bonds, or the correct adjustment of the hydrolysis
conditions can be used to avoid phase separation.
The formation of homogeneous and optical transparent
hybrid materials by the bulk free radical polymerization of
HEMA, simultaneously with the sol gel reaction of TEOS
as precursor is an example in using the advantage of an
attracting interaction [50,51]. The resulting materials were
characterized by DSC, SEM, TEM, SAXS, and DMA
measurements. From these measurements, it was concluded
that the two systems form a bicontinuous, truly interpenetrating material. Additionally, SAXS, SANS, and TEM
88
Scheme 2.
studies on a HEA/TEOS system revealed that there is a

dramatic change in the micromorphologies if the relative
rates of the two polymerization processes are changed in
such a way that when the sol gel polymerization is faster
the phases are more finely dispersed. If covalent bonds were
introduced between the two phases, the homogeneity of the
material was further improved [52].
Polyimidesilica gel hybrids have been prepared by the
simultaneous formation of polyimides and a silica network
formed in a solgel process. The hydrolysis and condensation
of TMOS was carried out in a solution of N,N-dimethylacetamide (DMAc) containing 5% LiCl, CaCl2 or ZnCl2, and a
polyimide intermediate. Films were cast from the resulting
mixtures and the solvent was gradually evaporated. The
results of this procedure were clear, transparent, pale yellow
or amber-colored hybrid films in which the salts were
dispersed at the molecular level. Pyrolysis of the composites
at 600 8C gave mesoporous silica [53]. Thermoresponsive
composites were obtained from the in situ polymerization of
N-isopropylacrylamide, methylenebisacrylamide, and
TMOS. The resulting hybrid materials showed a swelling
behavior typical of interpenetrating polymer network structures. The polymer hybrid materials swelled in water, and the
degree of swelling decreased continuously with increasing
temperature. The cleavage of interactions of the poly(Nisopropylacrylamide) chains was observed as an endothermic
peak in the DSC plot [54].
Besides the use of monomers with strong interactions to the
solgel network forming species, hydrophobic systems such
as poly(St) can also be homogeneously incorporated into such
materials by tuning reaction conditions such as the solgel
catalyst concentration [55,56]. Another method of inducing
attractive interactions between the organic polymer and the
solgel derived SiO2 species is the incorporation of organic
groups in the SiO2 network using trialkoxysilanes. Even pp

interactions between poly(St) and phenyltrialkoxysilanes
seem to improve the positive interactions [57].
Non-shrinking nanocomposites have been produced via
different approach [58 61]. Silicon alkoxides possessing
polymerizable alkoxy groups have been synthesized. The
alkoxy groups were liberated during the sol gel processing
as the corresponding alcohol (Scheme 2). Aqueous ringopening metathesis polymerization (ROMP) [62] as well as
free radical polymerization were used for the organic
polymerization reaction.
2.4. Dual network precursors
The network forming functionalities can also be covalently
connected to each other. This is realized in two different ways:
(i) functional groups for the organic and inorganic polymerization/polycondensation process are incorporated in one
molecule or (ii) functional groups for the second polymer are
incorporated in a preformed polymer of the other type. Typical
examples for bifunctional precursors are the commercially
available molecules GLYMO or MEMO (Scheme 3). These
systems allow either a simultaneous or a sequential formation
of two networks. Furthermore, a preformed network or
polymereither inorganic or organiccan be functionalized
with pending functional groups capable of forming the second
network. Another possibility of forming such materials is the
preparation of organic polymers, which were initiated or
quenched by a species that allow the incorporation into sol
gel networks (end-capped polymers) (Scheme 4).
Triethoxysilyl mono- and di-terminated polyoxazolines
were prepared by quenching the polyoxazolines either by
amine functionalized trialkoxysilanes or by unsaturated
amines, which were then subjected to hydrosilation with
Scheme 3.
89
Scheme 4.
trialkoxysilanes. These triethoxysilyl-terminated polyoxazolines were either used to surface-modify silica gels, or for
acid-catalyzed sol gel reactions [63 66].
Unsaturated monomers such as MEMO or styrylethyltrimethoxysilane have been homo- or copolymerized with
methyl methacrylate [67 73], styrene [69,74 76] or
acrylonitrile [77] (Scheme 5). The functionalized polymer
chains were hydrolyzed and cocondensed with TEOS and/or
other precursors for the formation of the inorganic network
via an acid-catalyzed sol gel route. The lack of welldefined glass-transition temperatures for the polymers in the
silica matrix revealed that the polymer chains were
uniformly distributed in the materials. Accordingly, the
poly(MMA) SiO2 as well as the poly(St) SiO2 hybrid
materials had an excellent optical transparency.
The solgel process of transition metals such as titanium,
zirconium, or vanadium is very fast compared to that of
silicon, and therefore a better control over the polycondensation is required to obtain homogeneous composite materials
in a simultaneous inorganic and organic polymerization
reaction. This can be achieved via a partial substitution of
alkoxides groups in the precursors by stronger complexing
ligands such as bidentate systems. As dual network forming
precursors they also have to contain a functional group which
is able to react in an organic polymerization, for example, a

ligand such as acetoacetoxyethyl methacrylate. This method
was used in the copolymerization of methacrylate with
titanium, zirconium, or vanadium precursors resulting in
hybrid organicinorganic copolymers intimately interpenetrated on a nanometer scale [7880].
3. Incorporation of metals and metal complexes in

polymers by coordination interactions
Although the inclusion of metals in polymers occurs
usually on the molecular scale and therefore these systems are
not covered by this review, this section was added for the
completeness of this paper. Furthermore, based on the long
lasting investigations of such systems, they can be helpful to
understand the mechanisms, e.g. nucleation in a polymeric
matrix, of other inorganicorganic hybrid species and they are
potential precursors for metal cluster containing polymers.
Methods for the inclusion of metals in organic polymers are
the: (i) polymerization and copolymerization of metalcoordinating monomers, (ii) coordination of metals to
preformed polymers, (iii) direct incorporation of the metal
into the polymer chain, (iv) incorporation of the metal into
Scheme 5.
90
plasma polymers, and (v) mechanochemical synthesis [81].

Although all of these techniques lead to polymeric products
with metal inclusion, the latter two are only discussed for
completeness, and the interested reader is referred to other
reviews in this field [81,82]. Consequently, the area of socalled metal centered macromolecules, which has been a new
subject in research in recent years, will be reviewed here.
3.1. Coordination of metals to the polymer backbone
The major interactions that can be used for the
incorporation of metals in polymers are the use of functional
groups to form coordination compounds. All types of
interactions suitable to form a metal complex can be
applied. Due to their Lewis basicity poly(vinyl pyridines)
[83], poly(vinyl amines) [84] or poly(L -histidine) [85], as
homo- or copolymers, have a high affinity to coordinate
metal ions such as Zn [83], Ni [86], Co, Ru [87], Pd [88], or
lanthanides [89], which were incorporated as salts. The socalled coordination crosslinking takes place if the polymer
coordination sites displace the ligands of the metal salt or
complex. Examples include the replacement of the acetonitrile ligands in bis(acetonitrile)dichloropalladium, or
coordinated water molecules in cobalt salts by p-bonds in
the polymer backbone. The incorporation of such metals
leads to drastical changes in the properties of the polymers
such as an increasing Tg [84].
Palladium salts incorporated into a polyolefin containing unsaturated side groups such as polybutadiene or
polyisoprene can cause crosslinking between the polymer chains by palladium catalyzed Heck-type reactions.
This methodology used to obtain crosslinked polymeric
systems is called reactive blending [88,90,91]. The
swelling behavior of such crosslinked systems is
dependent on the salt concentration and decreases with
increasing palladium content. The mechanical and
thermal properties of the resulting polymer blends
such as an enhanced stress strain behavior, an increase
in Youngs modulus as well as an increase of Tg up to
100 8C depending on the PdCl2 content [92], and the
annealing process is significantly influenced by the Pd
content [93]. In addition to the formation of crosslinked
systems, transition metal additives can also help to
compatibilize polymeric mixtures which would otherwise exhibit phase separation [87,90,91,94,95].
3.2. Metal-coordinated monomers
A useful way to incorporate metals into polymers is the
use of metal-coordinating monomers in the polymerization
reaction. Polymerization and copolymerization of such
compounds has already attracted much interest in the
literature [81,96 101]. Many of the metal-containing
polymers have only short chains, possess very poorly
defined structures, and/or are often insoluble in common
organic solvents as a result of intermolecular forces between
single chains or crosslinking by bridging coordination sites.

In the past, this often led to a poor characterization of these
interesting materials. In principal two different polymer
systems can be distinguished: those in which the metal is
part of the polymer chain and others in which the metal is
coordinated to pendent groups. There are a huge number of
possibilities using combinations of different ligands and
metals, as a result this review will give only a short
overview of possible monomers which have already been
discussed in the literature. In Scheme 6 possibilities for
polymers with metals in the chain and a selection of
potential metal-coordinated monomers used in polymerization reactions is shown. References for these systems can
be found in the cited reviews.
3.3. Metal-centered polymers

In recent years, a new type of metal-centered polymeric
systems was developed, the so-called metal core macromolecules. In this approach, a metal is coordinated with
ligands that include functional groups that are able to initiate
a polymerization reaction, or that can be transformed to
have such a functionality [102 105]. Fe(II) and Ru(II)
complexes, with one to three (4,40 -halomethyl)-2,20 -bipyridine (bpy) ligands, have been used to initiate living cationic
oxazoline polymerizations (Scheme 7) [102,104,105]. The
polymerizations yielded hybrid systems with molecular
weights from 1600 to 4600 and low polydispersities. The
obtained polymers revealed the same UV/VIS absorptions
as the initiators indicating that the polymers were still
coordinated to the metal via the initiating ligands.
Disassembly of the metal core has been achieved under
various conditions. For example, treatment of the iron
complex with aqueous K2CO3 yielded a colorless solution
with concomitant precipitation of an iron oxide/hydroxide.
The original violet color of [Fe(bpy)3]2 was shown to be
restored by treatment of the solution with (NH4)2Fe(SO4)2,
which revealed that the bpy terminated polymers reassemble
around the iron center. By using different oxazoline
monomers, i.e. 2-ethyl-, 2-undecyl- or 2-phenyl-2-oxazoline, amphiphilic metal-centered six-arm star block copolymers have been prepared [104]. A similar approach was
used to prepare 6,60 -bisfunctional 2,20 -bipyridine copper
complexes as initiators for the living cationic polymerization of 2-ethyl-2-oxazoline [106]. Block copolymers with
poly(2-phenyl-2-oxazoline) as the second block were also
synthesized by the same method. This study was extended to
(5-bromomethyl-50 -methyl)-2,20 -bipyridine as a ligand for
Co(II), Fe(II) and Ru(II) to form initiators for living cationic
polymerization of 2-oxazolines [107]. Ru(II) complexes
bearing one to three chloromethyl functionalized bpy
ligands have been used as ATRP-initiators in styrene
polymerizations producing Ru(II) core complexes with
two, four, and six arms [103,108].
91
Scheme 6.
4. Intercalation in 2D layered materials

Considerable interest has concentrated in the last
decades on the insertion of polymers into host lattices due
to the unique properties of the resulting materials.
Composites from inorganic layered lattices with polymers
have been known for quite a long time and this review can
only introduce this very broad research field. Readers who
are more interested are referred to more detailed reviews and

references therein [109 114]. Classically inorganic 2D
mineral lattices have been used as fillers. They were
incorporated into polymers to improve the bulk properties
such as shrinkage on molding, stiffness, heat resistance, and
flammability, decrease of electrical conductivity, or permeability for gases such as oxygen or water vapor [115,
116]. In recent years these classical applications expanded
92
Scheme 7.
based on special properties, e.g. the higher degree of

ordering of the polymers between the layers, or optical,
mechanical, and electronic properties, in the region of
sophisticated high-tech materials with possible applications in lots of different areas.
There are several procedures to incorporate inorganic
layered 2D materials finely dispersed into a polymer matrix.
In principal these can be distinguished using the following
classification: (i) intercalated hybrids in which one or more
molecular layers of polymer chains are inserted between the
sheets or galleries of the inorganic host, (ii) delaminated
hybrids in which the layers are exfoliated (or delaminated)
and homogeneously dispersed in a polymer matrix, or (iii)
systems between the two extremes (Scheme 8) [109,111].
Contrary to intercalated systems the exfoliated hybrids only
contain a small weight percentage of host layers with no
structural order. To obtain polymer systems reinforced by
single sheets from mineral clays, the reaggregation of the
layers in the polymer matrix has to be prevented.
Principally, three methods for the formation of polymer clay nanocomposites can be used.
(i)
Intercalation of monomers followed by in situ

polymerization.
(ii) Direct intercalation of polymer chains from solution.

(iii) Polymer melt intercalation.
Each of these methods has its advantages and disadvantages, for example, the in situ polymerization only works
with suitable monomers, or the intercalation of polymer
chains has a quite slow kinetics originating from diffusion
phenomena.
For the in situ polymerization, one can take advantage of
the oxidizing properties of some of the host lattices to
induce polymerization of suitable monomers. For example,
conjugated polymers such as poly(An), poly(Py), or
poly(Tp) were formed within the galleries of vanadium
oxide, molybdenum trioxide, tantalum sulfide, or vanadyl
phosphate [117 120]. The resulting materials are intercalated systems in which the polymers are located between
the layers. If the oxidation potential of the host itself is not
high enough molecular oxygen in the presence of redox
active host ions (e.g. Fe3, Cu2) can be used for the
oxidative polymerization process. This method has been
termed redox-intercalative polymerization.
Solution methods (either in situ polymerization or
solution intercalation) often require an exchange of the
metal cations, which could be located between the crystalline layers, by organic cations such as alkylammonium
93
Scheme 8.
cations. These cations lower the surface energy of the

inorganic host and improve the wetting characteristic of the
materials with regard to the polymer. Additionally functional groups, which allow a chemical reaction with
monomers, oligomers, or polymers and hence, improve
the adhesion between the inorganic phase and the polymer
matrix, can be introduced using the corresponding organic
cation. Applying these methods, composite materials such
as Nylon hybrids [121 123], epoxy resin materials [124,
125], or in situ poly(MMA) [126], and poly(caprolactone)
[127] polymerized systems have been produced with ionexchanged clays. Interactions of functional groups in
monomers such as maleic anhydride [128], or epoxy resins
[129] with the ionic surface of the clay galleries can support
the swelling of the clay and the polymerization of the
monomers can proceed between the galleries. Ionic
initiators for nitroxyl-mediated living free radical polymerizations were intercalated in the galleries of montmorillonite, followed by a polymerization of styrene. The
resulting nanocomposite contained the silicate randomly
dispersed spatially and directionally in the polystyrene
matrix. The polymer was desorbed from the silicate and
analyzed. The resulting molecular weight and molecular
weight distribution showed that a well-controlled polymerization occurred between the layers [130]. Even
polyolefins, such as polyethylene, have been polymerized
in situ between the layers of a fluorohectorite using a
cationic palladium catalyst [131]. Many of the in situ
polymerization techniques subsequently completely separate the layers from each other and/or form the hybrid matrix
material with homogeneously distributed platelets.
The incorporation of preformed polymeric chains from
solution between the sheets of the minerals may also result
in intercalated composite materials. If this procedure is
applied, the polymer has to be soluble in a solvent which can
fill the space between the layers. In most of the cases, a polar
solvent is required which helps to swell the clay and, in
some cases, leads already to a total exfoliation resulting in
solvent dispersed single-sheet colloids. Additives such as
long-chain alkyl amine or ammonium salts can also be used
to separate the layers. Poly(EO) of molecular weight 105 has
been intercalated between the galleries of montmorillonite
using polymer solutions in H2O, MeOH, or acetonitrile
[132]. This study showed that the nature of the solvent is
crucial to facilitate the insertion of organic materials
between the layers. Based on the different polarity of the
solvents, a different degree of swelling is reached and thus
an easier incorporation of the high molecular weight
macromolecules. Water-soluble polymers such as
polydiallylamine [133], poly(NVP) and poly(4VP) [134]
have been intercalated into the layers of different inorganic
materials. Generally, surfactants, such as amphiphilic block
copolymers, can also be used to support the swelling of the
layered material and additionally serve as compatibilizers
between the hydrophilic surface and hydrophobic polymers.
Employing this universal approach, it is possible to combine
94
nearly any kind of inorganic material with any kind of

polymeric material by tailoring the compatibilizing
macromolecule in the correct way. For example, block
combinations such as poly(EO)-b-poly(St), poly(EO)-bpoly(MMA), poly(MMA)-b-poly(MAc), or poly(St)-bpoly(2VP) have been used as compatibilizing agents in the
formation of composite poly(St) and poly(MMA) materials
[135,136].
Another possibility to introduce an otherwise incompatible polymer into the layered inorganic material is the
functionalization of the polymer with groups that allow an
easy incorporation of the polymer followed by a posttreatment to remove the functionalization. Poly(PV) has
been integrated in MoO3 using poly( p-xylene-a-dimethylsulfonium) chloride as precursor which can easily be
intercalated followed by heat treatment to convert the
precursor into the final polymer [137]. Polypropylene was
intercalated into montmorillonite using either functionalized
random or diblock copolymers and common organomodified layered systems, or by using neat/unmodified
polypropylene and a semi-fluorinated organic modification
for the silicates [138].
Especially with respect to environmental issues, the
direct melt intercalation into layered host lattices is the
preferred process for the formation of hybrid materials. This
process is based on the heating of a mixture of the polymer
and the layered system above the Tg, or the melting
temperature (Tm) of the polymer, and the diffusion of the
polymer between the galleries of the layers. With such a
method, poly(EO) [139] was incorporated in different host
lattices. The process was enhanced again using long-chain
alkyl ammonium ions, which were preintercalated into the
inorganic material. Even unpolar polymers such as poly(St)
have been intercalated into montmorillonite by melt
intercalation [140]. The poly(St) was afterwards deintercalated by suspending the hybrid in toluene.
5. Intercalation in 3D frameworks: zeolites, molecular

sieves and M41S-materials
Zeolites are crystalline aluminosilicates with welldefined pores smaller than 2 nm. There are a variety of
naturally occurring as well as synthetic zeolites. Zeolites
have attracted much interest as catalysts and adsorbents due
to their thermal stability and intraporous acidity. Molecular
sieves are also crystalline framework materials, but of a
non-aluminosilicate nature. M41S-materials belong to the
class of mesoporous three-dimensional (3D) solids with
ordered porosity in the pore size range 2 10 nm. Due to
their special properties, such as the controllable pore size,
there is a plethora of possible applications of these materials
[141,142]. All these porous inorganic solids are excellent
hosts for intercalation reactions because they contain welldefined empty pores and channels. A unique feature of these
materials is their ability to discriminate between shapes and

sizes of molecules. Therefore, the design of new materials
requires a match of the features of the guest with those of the
host. Contrary to the layered materials, which are able to
delaminate completely if the forces produced by the
intercalated polymers overcome the attracting energy of
the single layers, this is not possible in the case of the stable
3D framework structures. The obtained composites can be
viewed as host guest hybrid materials. There are two
possible routes towards this kind of hybrid material: (i)
direct threading of preformed polymer through the host
channels (soluble and melting polymers) which is usually
limited by the size, conformation, and diffusion behavior of
the polymers, and (ii) the in situ polymerization in the pores
and channels of the hosts (Scheme 9).
Hybrid inorganic organic materials from zeolite 13X,
and crosslinked or linear poly(St) and poly(EA) were
prepared. It was shown that two different composites were
formed, the so-called pseudo-interpenetrating polymer
networks (PIPNs) and full IPN. The PIPNs were formed
when no crosslinking compound such as ethylene glycol
dimethacrylate was added, while IPNs were formed in the
presence of these species [143]. An easy way to distinguish
between the two types of hybrid materials is the extraction
with suitable solvents. While the polymer chains could be
partially or completely removed from the PIPNs, this was
not possible in the case of IPNs. From the results of different
characterization methods, such as SEM, SAXS, DSC and
solid-state 13C NMR, it was concluded that some of the
poly(St) chains are incorporated within the internal 3D
channels of the zeolite particles [144,145]. The DSC studies
revealed that poly(St) incorporated in the channels of the
zeolite 13X did not show a bulk Tg which is consistent with
studies of poly(St) intercalated into layered silicates [146].
This observation is traced back to a possibly more extended,
one dimensionally oriented polymer chain conformation
which does not exhibit a bulk Tg. A surface-mediated
cationic polymerization technique was applied for the
formation of poly(PVE) HY zeolite hybrid materials
containing polyenylium sequences [147]. The zeolite
polymer hybrids had similar properties than the clay
polymer hybrids. For example, the conductivity of
a polyethyleneoxide/LiBF4 system was increased by two
orders of magnitude through inclusion in a zeolite [148].
Special properties of zeolites such as their active sites in
their cavities or the ability to entrap molecules of the right
size in their channels and pores can be used to form
materials which cannot be prepared from other porous
solids. The active sites often play a major role in catalytic
processes for which zeolites are well known. This particular
property can be utilized in the synthesis of hybrid materials
when employing acid catalyzed polymerizations, such as the
acetylene polymerization with H-ZSM-5 zeolite [149].
Organic chromophores have been trapped in zeolite cages
and afterwards embedded in a polymethacrylate matrix
95
Scheme 9.
[150]. To obtain high optical transparency the refractive

index of the polymer was adjusted to those of the zeolite.
The active protons of HY zeolites were used for cationic
polymerizations of several vinyl monomers inside the pores.
In porous materials where no such protons are present, such
as MCM-41, arylmethylium was incorporated. Utilizing this
method the synthesis of well-defined poly(vinyl ethers) or
poly(vinylcarbazole) under conditions of constricted geometry can be achieved [151].
Poly(PV) was incorporated in the most prominent and
most studied mesoporous silica material MCM-41 by an in
situ polymerization of xylene bis(tetrahydrothiophenium
chloride). The polymerization was most likely initiated by
deprotonated surface hydroxy groups and took place in the
pores of the material. The obtained powder showed the
typical luminescence behavior of PPV. The advantage of
the resulting material is that the quenching of photoluminescence, which is based on interchain interactions of the
polymer chains, is decreased [152]. A cationic polymerization of cyclohexyl vinyl ether (CHVE) was achieved using
triphenylmethylium or bis(4-methoxyphenyl)methylium
silanolate ion pairs, as well as mobile acidic silanols as
initiators. Depending on the initiation mechanism, different
structures of the polymer were obtained in the channels of
the material [153]. For a better adhesion between the pore
walls and the incorporated polymer, the pore wall of the
MCM was functionalized with methacrylate groups during
the synthesis of the silicate material. Different characterization methods showed that the methacrylate groups are
readily and completely accessible. Adsorbed MMA was
polymerized in the pores resulting in an inorganic organic
hybrid material [154].
Porous inorganic structures can serve as templates for
well-defined conducting structures of nanometer dimensions
such as molecular- or nano-wires. Therefore, different
types of conducting polymers have been prepared in the host

channels of these inorganic materials. Poly(An) was
synthesized in the channels of mordenite, MCM-41 and
zeolite Y [155 157]. The monomer was intercalated from
solutions or vapor phase adsorption followed by oxidative
polymerization in the presence of Cu(II), Fe(III), or
persulfate. A similar approach was used to incorporate
and polymerize acrylonitrile in the channels of MCM-41.
Pyrolysis of the intrachannel polyacrylonitrile results in the
formation of encapsulated of graphite-type carbon wires
[158].
Poly(Py) and poly(Tp) have also been successfully
included in the channels of different porous hosts [159,
160]. The conductivity of the obtained polymer filaments in
the host was studied by contactless microwave absorption.
6. Incorporation of inorganic particles and clusters

Physical mixtures of organic polymers and preformed
inorganic particles may lead to separation in discrete phases,
resulting in poor mechanical, optical, electrical, etc.
properties. In addition, particle agglomeration tends to
weaken mechanical or optical properties of the resulting
materials. The latter problem especially is observed in a
variety of hybrid systems in which clusters and particles are
involved. Unmodified inorganic particles tend to aggregate
in the polymer matrix independent of the kind of material
and the size. To avoid these drawbacks different methods
can be applied, for example, the use of functional polymers
[161] which interact with the surface of the particles, or
surface modification of the particles to change their
character.
96
6.1. Incorporation of unmodified particles

Nanocomposites based on nanosized inorganic particles
and clusters are an emerging field of research activity due to
the interesting properties of the particles, such as their
behavior as quantum dots or their possible super-para and
super-ferromagnetism, in combination with the other
properties of the materials including, for example, their
optical transparency. Another advantage of such hybrid
composites of particles in an organic polymer matrix is the
possible protection of systems that are sensitive towards
environmental conditions (oxygen, humidity, etc.) by
coverage with a protecting polymeric skin or inclusion in
a polymeric matrix [7]. Furthermore, the content of the
inorganic moiety can be gradually changed in the polymeric
matrix. Ordering in such systems also plays a role, from
highly ordered superlattices to so-called stochastic mixtures
where the particles are randomly dispersed. Therefore, the
possibilities for these materials cover a wide range of
applications with many yet unknown future perspectives
[82].
In principle, there are five possibilities to overcome the
phase separation in hybrid particulate systems: the use of a
polymer which interacts (van-der-Waals, dipolar, hydrogen
bonds, etc.) with the particles; the covalent attachment of an
inert organic layer on the surface of the particle core that
serves as a compatibilizer at the particle/polymer interface;
the encapsulation of the particles by special polymerization
techniques such as emulsion polymerization; the attachment
of functional groups which allow a covalent linkage with the
polymer; or the attachment of initiation groups for grafting
of polymer chains from the particle surface.
6.2. Encapsulation of particles in a polymer shell
Encapsulation of small inorganic particles by a polymer
layer, so-called core shell particles, can be carried out
applying an emulsion polymerization process. Polymerization occurs primarily at the surface of unmodified particles
due to the adsorption of the monomer on the surface,
followed by polymerization in the adsorbed layer
[162 164]. The formation of an initial hydrophobic layer

on the surface of the particles seems to be crucial for the
formation of the polymer shell. Methods for the introduction
of such a layer include the use of non-ionic surfactants,
amphiphilic block copolymers, etc. Furthermore, these
surface-active molecules fulfill another task: they avoid
agglomeration of the particles. The concentration of such
compatibilizing molecules in solution needs to be tuned
carefully because a latex formation in free micelles in the
emulsion can be observed at higher concentrations.
Additionally these molecules are usually only weakly
bonded to the surface and can therefore desorb easily.
Hence, the covalent attachment of organic groups, which
potentially can interact in the polymerization reaction, is
used for surface modification [165 170]. Using a one-pot
process, nanosized, surface-modified silica particles encapsulated with a polymeric layer have been formed (Scheme
10). Depending on the reaction conditions like stabilizer
concentration, different products were obtained, e.g. those in
which a few particles were encapsulated in a polymer shell
and those where only single shell particles were formed.
Additionally, pure polymer latex particles can also be
formed in the emulsion.
Not only the nanosized particles themselves are interesting systems, but also materials formed by their assembly.
The formation of so-called colloidal crystals is a challenge
because the self-organization is strongly dependent on the
size distribution that influences the formation of the packing
pattern, as well as on the surface functionality influencing
the interactions between the particles [171]. The resulting
materials can have feature sizes of the wavelength of
electrons, photons, or both, and they are interesting
materials for optics, electronics (photonic crystals, quantum
dot or dielectrical lattices), or chemical sensing [172].
3-(Trimethoxysilyl)propyl coated silica particles were
prepared by the Stober method [173,174] followed by a
surface-modification [175]. These particles were selfassembled in a film and UV copolymerized with different
monomers such as MA, MMA, HEMA, and TFEA. The
systems were able to selectively filter light with a bandwidth
less than 20 nm [176].
Scheme 10.
6.3. In situ growth of inorganic particles in a polymer matrix

The thermal decomposition of volatile metal compounds
in a polymer matrix leads to the formation of zero valent
metal particles, or particles of their oxides dispersed in the
polymer. Stable homogeneous dispersions of a variety of
metals have been obtained by this approach. For the
formation of homogeneous dispersions, it is important to
have some kind of interaction between the metal complex
and the polymer matrix. This is achieved either by the direct
coordination of the metal complex to amino or hydroxyl
groups, etc. in the polymer, or by the substitution of a labile
ligand in the metal complex with unsaturated groups in the
polymer (poly(St), polybutadiene, etc.) during the thermal
decomposition of the complex. Probably the best-studied
metal polymer composites obtained by this thermal
decomposition route are cobalt and iron carbonyls in the
presence of polymers such as polybutadiene, poly(St),
polypropylene, different block copolymers, etc. [177 179].
The size of the metal nanoparticles formed in the polymer
matrix depends on the reaction conditions, for example, the
thermolysis temperature or the solvent. Additionally, the
number of polar groups on the polymer backbone seems to
be important for the particle size; the more polar the groups,
the smaller the particles [82]. Instead of the metal carbonyls
other organometallic species can also be used as precursors
for the metal species in the composite materials.
Another method to obtain polymer-immobilized nanoparticles is the reduction of metal salts from solutions or
suspensions in the presence of a polymer, or of mononuclear
metal complexes bonded to the polymer. This method was
used in the production of composites containing Pd and Au
nanoparticles in a synthetic rubber film [180]. The reduction
can be carried out by agents such as hydroquinone, pphenylenediamine, pyrogallol, hydrogen, etc. [82]. Electrochemical methods [82], radiation-induced or photochemical
reduction are sometimes preferred to hydrogen reduction
[181]. The polymer metal interaction is an important
parameter in all these syntheses especially for the size and
size distribution of the metal particles as well as for their
dispersion. The polymer often plays the role of a ligand
which helps to avoid the association of complexes and
therefore limits the size of the formed particles. Furthermore, the interaction between the polymer and the metal
particles stabilizes the latter and helps to prevent their
oxidation.
Iron oxide nanoparticles were incorporated in a poly(An)
matrix adding iron salts to the polymer and subsequently
changing the pH to alkaline conditions by adding a base.
The obtained materials showed ferromagnetism [182,183].
A quite new method for the in situ generation of particles
in polymers is the use of specific structures formed by the
macromolecules, for example, the use of supramolecular
arrangements of block copolymers that form micellar
nanoreactors or the application of particular shaped
macromolecules such as dendrimers.
97
Gold nanoparticles were formed within the microdomains of a poly(St)-b-poly(2VP) diblock copolymer in the
presence of additional Py. The polymerization of Py was
effected by HAuCl4, which simultaneously generated Au
nanoparticles [184]. Thus, Au-poly(Py) nanocomposite
core shell particles were formed which was confirmed by
TEM measurements.
Crosslinked polymer matrices were used for the in situ
growth of magnetic g-Fe2O3 nanoparticles. The resulting
nanocomposites were transparent due to the small metal
oxide particle size, and the magnetization of the nanocomposite was greater by more than an order of magnitude than
those of the strongest room-temperature transparent magnets [185,186].
One of the challenges in nanochemistry is the production
of specific nanoscale objects in unlimited quantities. This is
due to the fact that control of the critical nanorange length
means control of new macroscopic properties. Dendrimers
as monodisperse macromolecules can fulfill the demands of
precursors for such materials. Dendritic molecules are
formed by connectors and branching units built around a
small molecule or a linear polymer (core) which leads to a
spherical or rod-like macromolecule. Based on the high
level of synthetic control, these systems are well defined in
their molecular weights as well as in their functionalities.
For example, depending on the final step of the synthesis the
interior and exterior can be very different, e.g. hydrophilic
and hydrophobic. These special properties make dendrimers
ideal systems for hosts in the formation of nanoparticles. In
a typical process of the formation of metal nanoparticles
metal ions are preorganized by the dendrimer molecule and
subsequently immobilized in or on the macromolecule. Size,
shape, size distribution, and surface functionality of the
metal nanoparticles are determined by the dendritic
template as well as by the chemistry of the preorganization
and immobilization process. Mesoscopically ordered hybrid
materials were formed using functional dendrimers and the
titanium oxo cluster [Ti16O16(OEt)32] as nano building
blocks. The two components were crosslinked through
covalent bonds formed by nucleophilic reactions between
the functional tips of the dendrimers and the titanium centers
of the clusters [187].
6.4. Surface-modification with polymerizable groups
Research in this area spans the modification of
commonly used inorganic fillers or particles, up to the
recent commercial availability of a variety of polyhedral
oligomeric silsesquioxanes (POSS), R8Si8O12 nanoclusters
(Scheme 11).
There are two principle possibilities to functionalize the
inorganic species with organic groups: (i) grafting
functional organic groups onto the surface of preformed
clusters or particles, and (ii) in situ functionalization of the
clusters or particles during their formation. The advantage
of the first method is that the inorganic particles can be
98
Scheme 11.
prepared by well-established techniques. However, for a

covalent modification of the surface reactive groups, such as
hydroxy groups or coordination centers, must be available.
Sometimes, especially in the case of clusters, the modification by organic moieties may require a rearrangement of
the surface groups. Another possibility for surface-modification is the attachment of organic groups by ionic
interactions. In the in situ-functionalization method, the
particles are formed in the presence of functional molecules,
which serve to cap their surface. An additional parameter
which has an important influence on the properties of the
final hybrid materials is the number of reactive functional
groups available on the surface. If only one group is present,
the particulate systems can be used as monomers to form
linear polymers; more than one functionality leads to
crosslinked systems (Scheme 12) [188,189].
Metal oxide clusters. Although there are many organometallic clusters with potential polymerizable ligands such
as acrylate, vinylpyridine, vinylimidazole, acrylonitrile, etc.

they were only rarely used as monomers in polymerization
processes [82]. In these polymerizations the interaction of
the polymerizing species with additional ligands coordinated to the metal was often observed which led to difficult
to characterize materials. Metal oxide clusters have recently
been investigated due to their interesting optical, electronic,
and magnetic properties. The heterotungstate cluster
K4[SiW11O39] was derivatized by reaction with various
trichloro- or triethoxysilanes RSiX3 (X Cl or OEt)
containing polymerizable groups R (R allyl, vinyl, styryl,
or methacrylate) [190,191]. Two functional groups per
cluster unit were thus introduced, and the obtained anionic
clusters had the composition [SiW11O39(OSi2R2)]42. The
polymerizable groups bonded to the surface were used for
crosslinking the clusters by free radical polymerization in
solution (without the addition of organic monomers). Their
reactivity was found to be similar to that of the corresponding silanes and increased in the order R vinyl (polymerization yield 5% in DMF) ! allyl (20%) , methacryl
(65 70%) , styryl (100%). The hydrodynamic radius of
the obtained inorganic organic hybrid polymers varied
between 5 and 120 nm, but did not always correspond to the
polymerization yields. 29Si NMR, UV spectroscopic
investigation, and cyclic voltammetry studies showed that
the structural integrity of the clusters was preserved upon
polymerization and that the clusters retained their typical
redox and optical properties in the polymers.
This work was extended by similarly functionalized
polyoxotungstate cluster for the crosslinking of organic
polymer chains. The cluster [g-SiW10O36(OSi2R2)]42 (R
[CH2yCMeC(O)OCH2CH2CH2]) was obtained by reaction
of [g-SiW10O36]82 with MEMO [192]. Functionalization
via both covalent and ionic interactions was achieved by
additionally employing the quaternary, methacrylate-substituted ammonium counter-ion [CH2yCMe C(O)OCH2CH2CH2NMe3]. These clusters were copolymerized in
Scheme 12.
99
Fig. 2. Surface-modified oxometallate compounds with (a) titanium or (b) zirconium as metal, and acrylate or methacrylate as polymerizable
group at the surface. These systems were used as crosslinking agents in polymerization reactions.
acetonitrile with ethyl methacrylate in different ratios (1:10

to 1:50), and swollen gels were obtained. The degree of
swelling increased with an increasing comonomer to cluster
ratio, i.e. dependent on the crosslinking density. Spectroscopic investigations again proved that the polyoxotungstate
was incorporated in the material without a structural change.
Oxo-hydroxo stannate clusters as building blocks for
hybrid materials were formed using the cationic cluster
[(BuSn)12O14(OH)6]2(OH2)2. Functional organic groups
were obtained by exchange of the hydroxide counter-ions
against methacrylate anions [193,194]. The methacrylate
anions not only interact with the cluster cation by Coulomb
interactions, but also by hydrogen bonding to the hydroxy
groups capping the cluster surface. Homopolymerization of
the functional clusters by free radical polymerization failed,
probably due to sterical hindrance between the macrocations. Free radical copolymerization with MMA in THF
(1:13 to 1:52 ratio) resulted in soluble inorganic organic
hybrid polymers.
A different approach for the functionalization of oxoclusters is the in situ modification during their formation.
This was mainly investigated for the preparation of
organically substituted oxotitanium and oxozirconium
clusters [195 199]. When titanium or zirconium alkoxides
M(OR)4 (M Ti, Zr), or mixtures of both, were allowed to
react with a defined excess of acrylic or methacrylic acid,
crystalline clusters of the general composition MxOy(OH/
OR)z(OOCR)w of differing size and shape were obtained
(Fig. 2). There are a variety of structurally characterized
examples with different morphologies. Copolymerization of
these clusters with MMA or MAc in ratios between 1:50 and
1:200 resulted in polymers in which the polymer chains
were efficiently crosslinked by the oxometallate clusters
[200 203]. Glassy, insoluble materials were typically
obtained upon copolymerization with MMA, and insoluble
powders with MAc. The specific surface area of the doped
poly(MAc) depended on the amount of incorporated cluster
and increased with an increasing cluster proportion. The
cluster crosslinked poly(MMA) was insoluble in common

organic solvents, but swellable. The solvent uptake upon
swelling increased with an increasing comonomer to cluster
ratio. The thermal stability of poly(MAc) and poly(MMA)
was improved by the cluster crosslinking, and the thermal
depolymerization observed in the undoped polymers was
inhibited.
Doping or crosslinking of organic polymers with
tungsten, tin, zirconium or titanium oxide clusters can be
considered an extension of the so-called POSS reinforced
polymers, in which silicon oxide clusters are incorporated
into organic polymers. Variation of the inorganic building
blocks by using transition metal oxide clusters could
possibly widen the range of properties of these inorganic
organic hybrid polymers.
Silsesquioxanes cubes. Probably, the most prominent
representatives of cluster-like inorganic components are the
silsesquioxane cubes. These systems are obtained as monoor octafunctionalized systems.
Octafunctionalized cages such as the anionic oxyfunctionalized system (SiO2.5)82
8 or the octahydrido species
(HSiO1.5)8 are obtained in reasonable yields and have been
used as precursors for multifunctionalized crosslinking
agents. Functionalization of the (SiO2.5)82
8 cube is carried
out by quenching the anionic silsesquioxane with ClSiMe2H
and further hydrosilation. The octahydrido compound can
be prepared by slow hydrolysis of HSiCl3 and functionalized by hydrosilation. The Pt-catalyzed hydrosilation of
(HSiO1.5)8 and (H(CH3)2SiOSiO1.5)8 with propargyl methacrylate occurred specifically at the propargyl site retaining
the methacrylate functionality for subsequent polymerization [204]. The silsesquioxane cubes were hydrosilated
with allyl glycidyl ether in a similar way [205]. A different
approach to such crosslinking species is the epoxidation of
vinyl-substituted cubic polyhedral silsesquioxanes with
m-chloroperoxybenzoic acid which can be directed to a
partial, or full epoxidation of the vinyl groups [206]. The
crosslinking components received from this reaction are
100
soluble in organic solvents, e.g. THF, toluene, hexane and

CH2Cl2, and were used in thermal and photochemical
polymerizations to give hard, abrasion resistant, insoluble
composites containing up to 65 wt% silica.
In recent years, POSS inorganic organic hybrid
polymers have been developed up to a commercial scale.
The chemistry of these systems is based on the design of
well-defined inorganic oligomers with only a single
polymerization or initiation site per cluster. Each of these
clusters has an inorganic silica-like core and is surrounded
by eight organic groups, seven of which are inert towards
polymerization and only one is active. Polymerization at this
single site results in a linear polymer with pendent inorganic
clusters of approximately 1.5 nm diameter. The unique
property of such materials is that there is no crosslinking and
the pending linear polymeric structure allows for an easier

processing and characterization of these systems by
conventional analytical methods compared to, for example,
IPNs. The modifications of polymers with these inorganic
building blocks have an influence on the thermal, oxidative
and dimensional stability of the linear polymer chains [207].
Different polymer backbones have been synthesized using a
variety of different substitution patterns at the silica cage
(Table 1).
Methacrylic-substituted POSS monomers were
synthesized by corner capping the trisilanol cages
R7Si7O9(OH)3 (R c-C6H11, c-C5H9) with methacrylate
containing trichlorosilanes (Scheme 13) [208]. Homoand copolymers of these systems reveal no thermal
transitions below their decomposition temperature of
Table 1
Different POSS compounds (RR7Si8O12) as monomers for copolymerizations
R0
Polymerization
Comonomers
Reference
ROMP
[212]
Free radical polymerization
[209]
Free radical polymerization
[210]
Epoxy resin formation
[207]
ATRP
[213]
Polyurethane synthesis
[211]
ZieglerNatta
Ethene, propene
[215]
101
Scheme 13.
388 8C. Styrylethyl-substituted systems were homo- and

copolymerized with styrene via a free radical polymerization initiated by AIBN [209]. A reactivity change of the
POSS macromers compared to styrene was not observed.
Generally, POSS inclusion changes the thermal properties
of the obtained polymers drastically towards thermally more
robust systems, and the Tg is efficiently enhanced upon
copolymerization with the associated POSS monomer.
Rheological measurements revealed that an increasing
proportion of POSS also affects the polymer dynamics
[210]. A high-temperature rubbery plateau developed at
higher concentrations of POSS, this has also been explained
by interchain interactions between the pendent inorganic
groups on the polymer backbone. The tensile modulus of
POSS reinforced polyurethanes was greatly increased by the
pendent inorganic molecules [211]. Morphological studies
by X-ray analysis on randomly copolymerized norbornene
POSS systems revealed that at higher concentration of
cyclopentyl-substituted systems more ordered regions,
probably caused by agglomerating POSS cages, were
present [212]. Homopolymers, diblock-, and branched
triblock copolymers with quite low polydispersities were
obtained from ATRP of methacrylate-substituted POSS
systems with methyl methacrylate and n-butyl acrylate
[213]. In addition substituted POSS was also used as an
initiator for ATRP [214]. Moreover, hybrid materials of
mono-functionalized POSS systems were obtained by
homo- or copolymerization via Ziegler Natta polymerization with olefins [215]. Besides the non-crosslinked
materials, epoxy resins with terminating POSS systems
were produced, and their thermal and mechanical properties
were investigated [207].
The POSS cages with one reactive substituent have
seven inactive substituents to increase the solubility,
usually cyclohexyl and cyclopentyl groups. These substituents lead to remarkable properties of the silica cages.
For example, the cyclohexyl-substituted system is twice
as soluble as the cyclopentyl-substituted cage [209].
Furthermore, a change of the size of substituents from
cyclopentyl to cyclohexyl also affects the Tg in such a

way that with the same amount of POSS, the cyclopentyl-substituted polymer has a much larger Tg than the
cyclohexyl-substituted macromolecule. These solubility
differences are believed to be based on the lattice energy
in the crystalline solid.
The systems discussed are representative examples of a
larger number of related studies, in which substituted POSS
have been applied as monomers to produce various
polymers with pendant POSS substituents. The common
feature of all systems is that several polymer properties are
promoted by the incorporation of POSS. Among other
properties, higher degradation and glass transition temperatures, reduced flammability, reduced viscosity, and higher
oxidation resistance are observed.
6.5. Surface-modification with initiating groups
Initiating groups attached to the inorganic core allow the
grafting of polymers from the surface of the inorganic
moiety. This approach has advantages over the more often
used grafting to technique where end-functionalized
polymers are grafted to the surface of inorganic particles,
i.e. leading to restrictions in the surface coverage. The
grafting from approach leads to particle-like structures,
which can be tailored by the size and functionality of the
inorganic core and/or the polymer shell. In principle, this
approach can be used for all kinds of inorganic cores
(Scheme 14). In every case, a key step is the attachment of
initiating groups onto the particle surface. The methods
described before used to attach the functional groups by
ionic or covalent bonds can be applied again. In most of the
work done in this area, polymers were grafted from
nanometer- and micrometer-sized silica particles
[216 219].
Free radical polymerizations. Diazo groups capable of
initiating free radical polymerization were attached to the
surface of pyrogenic amorphous silica (Aerosile) using a
multistep synthesis [216]. The silica surface showed a diazo
102
Scheme 14.
2.
group overage from 0.03 up to 0.1 diazo groups per 100 A
This means that only every 30th hydroxy group had reacted.
Poly(St) was grafted from the thus modified surface. It
should be noted that in free radical polymerizations with the
described macroinitiators, polymerization also occurs in the
solution because the surface-attached initiator decomposes
into two radicals from which one initiates polymerization in
solution. A linear dependence between the monomer and
initiator concentration and the polymer coverage was
observed. Termination of the grafting chains occurred due
to the lack of initiating radicals or sterical hindrance at the
surface. The molecular weight of the polymers cleaved from
the surface by HF treatment were up to 1.46 106, while
those of the homopolymers formed in the solution
simultaneously were up to 1.75 106.
In more recent studies, silane-coupling agents such as
alkoxysilanes [219 221] or chlorosilanes [217,218] have
been used to modify the surface of silica particles. For
example, 4,40 -azobis(4-cyanopentanoic acid) was immobilized on the surface of pyrogenic silica via amide bonds
through attached aminophenyltrimethoxysilane. The concentration of diazo groups at the surface reached 0.2 mmol/
g. DSC measurements proved that the stability of the
initiator decreased upon immobilization. Poly(MMA) with a
molecular weight of up to 8.7 105 was grafted from the
surface. The polymerization was highly affected by the
Trommsdorff effect [222] which was also made responsible
for the higher molecular weights of the grafted polymer
compared to the homopolymer.
Polyesters were grafted from various ultrafine inorganic
particles such as silica, titania and ferrite by anionic ring
opening copolymerization of epoxides and cyclic acid
anhydrides [221]. The silica, titania and ferrite particles had
sizes of 16, 120 and 15 nm, respectively, and surface hydroxy
group concentrations of 1.37, 0.77 and 0.55 mmol/g. The
initiating group was a potassium carboxylate, which was
attached to the surface by a series of modifications. The

amount of initiating groups on the surface of the silica,
titanium oxide and ferrite particles was 1.92, 0.94 and
0.62 mmol/g, respectively. The used organic monomers
were styrene oxide, chloromethyloxirane, gylcidyl methacrylate, gylcidyl phenyl ether, phthalic anhydride, succinic
anhydride, and maleic anhydride.
Surface anchored peroxide initiators were used for the
grafting of methyl methacrylate [221]. This type of initiator
was attached to the surface by treatment of silica particles
with thionyl chloride to obtain surface Si Cl groups, which
were then reacted with tert-butyl hydroperoxide or diisopropylbenzene hydroperoxide to form the initiating groups.
Depending on the type of peroxide, the concentration of
initiators on the surface was 0.08 mmol/g for tert-butyl
peroxide and 0.29 mmol/g for diisopropylbenzene peroxide.
Both peroxide groups were able to initiate the polymerization and led to the grafting of poly(MMA).
The study of the kinetics and mechanism of an azoinitiated free radical styrene polymerization from modified
silica particles was part of more detailed studies for the
grafting of polymers from surfaces [218]. In these studies
initiators with a cleavable ester group were attached to the
surface. After the polymerization, the ester group was
catalytically cleaved. The differences between the obtained
poly(St) homopolymer and the polymers obtained by
polymerization in solution were mainly due to differences
in the termination reactions. It was found that although the
initiator efficiency of surface-attached initiator is slightly
decreased, it still allows the formation of high molecular
weight polymer with high graft density.
ATRP. Contrary to free radical polymerizations, where
as discussed earlier, polymerization also occurs in the
solution, this is not the case for controlled radical
polymerization, such as transition metal-mediated ATRP.
With this technique poly(AA) was polymerized from silica
103
Fig. 3. Schematic representation of the formation of structured nano- or mesoporous materials by a self-assembly process of block copolymers.
particles for chromatographic applications [217]. [2-(m/pChloromethylphenyl)ethyl]trichlorosilane was attached to

the surface of a silica gel with a particle diameter of 5 mm
and a pore size of 86 nm. A dense 5.1 mmol/m2 monolayer
of the initiator was thus created. The film thickness of the
grafted poly(AA) was calculated to be 10 pm and therefore
would reduce the average pore size of the silica gel but not
block the pores. The modified silica was used as a solid
phase in size-exclusion chromatography and revealed a very
good separation behavior for a mixture of the four proteins
thyroglobulin, ovalbumin, ribonuclease A and aprotinin.
The elution times were much faster than with a commercially available silica-based stationary phase.
In another study, silica spheres with a diameter of 70 nm
were produced by the Stober process and modified by
reaction with the silane coupling agent [2-(4-chloromethylphenyl)ethyl]dimethylethoxysilane [219]. A surface concentration of the initiator of 0.14 mmol/g was thus achieved.
The obtained particles were used as macroinitiators for
ATRP of styrene. In a similar approach (110 -chlorodimethylsilylundecyl)-2-chloro-2-phenylacetate was covalently attached to the surface of commercially available
silica particles and ATRP grafting of styrene from the
surface was achieved. The grafted polymers were detached
from the solid particles for analysis. After polymerization of
a first generation of grafts and work-up of the hybrid
particles, the chain ends of the grafts were still active to
initiate a second monomer feed [223]. Furthermore, gold
nanoparticles were modified with thiole-functionalized
initiators for ATRP and BA was polymerized from the
surface [224].
7. Nanoengineering of composite materials

An important area with respect to potential applications
of nanocomposite materials is the ability to design these
materials in the nanoscale. The formation of hierarchically
well-ordered materials from the micro- to the nanoscale is
especially important for many possible applications. The
specific role of the polymer, for example, in structuredirection, is based on their properties, e.g. phase behavior,
which are often not available in the same broadness with
other templates.
Probably, the most prominent example is the formation
of nano- and mesostructured materials applying the selfassembly process of block copolymers. A milestone in the
formation of such materials was the discovery that in
addition to single molecules molecular assemblies, found,
for example, in liquid crystals, can be used for templating
inorganic matrices [225]. This supramolecular self-assembly relies on the ability of molecules such as surfactants to
self-assemble into micellar structures that, when concentrated, undergo a second stage of self-organization resulting
in liquid crystalline mesophases. Molecular inorganic
species can cooperatively assemble with these structuredirecting agents (templates) to form the mesoscopically
ordered inorganic backbone of the final material (Fig. 3).
Usually the intention of this preparation route is the
formation of porous, molecular sieve-like materials, which
can be obtained from the nanocomposites by removal of the
polymer template. In addition to the classical ionic
surfactants used, the application of block copolymers as
templates in block-selective solvents is an emerging field in
materials chemistry. The polymeric approach allows for the
extension of the size of the organized domains into larger
scale features, and the possibility to reach morphologies
which cannot easily be obtained with usual surfactants [226,
227]. A plethora of different polymers have already been
used as structure-directing media and therefore only a short
list of examples is given here: polybutadiene-b-poly(vinylpyridinium) [226]; anionic poly(ethylethylene)-b-polystyrenesulfonate [226]; poly(butadiene-b-ethylene oxide) [228];
ABC triblocks [229]; commercially available PEO-based
systems [230 233]. Besides block copolymers hyperbranched macromolecules also showed a structure-directing
ability [234].
The formation of the inorganic network is based, in most
of the cases, on the sol gel process already discussed. The
resulting porous materials attract interests, for example, for
their potential application as ultralow dielectric materials
for advanced microelectronic devices [234,235].
Most of the above-mentioned structured materials are
based on a silicate inorganic network, however, other metal
oxides were also the source of the inorganic framework.
Organically modified aluminosilicate mesostructures were
synthesized from (3-glycidyloxypropyl)trimethoxysilane
and aluminum-sec-butoxide with the use of isoprene
ethylene oxide block copolymers as the structure-directing
molecules [236 239].
104
Another approach to design the morphology on the nanoor mesoscale is the use of a 3D self-assembly of
nanoparticles for the formation of ordered materials in
such a way that the voids between the lattice were filled with
a material forming a rigid network. Two approaches can be
applied: (i) either the template is of organic nature and the
network formation occurs by inorganic processes, or (ii) the
templates are inorganic spheres and a polymer forms
the network. For the first approach mainly latex colloids,
such as crosslinked polystyrene, are used and the voids
between the nanospheres are filled with inorganic material
precursors. These materials have recently attracted much
interest due to their potential application as optical
waveguides [240].
A different method of preparing ordered composites is
the use of artificial 3D periodic opal lattices with silica
spheres smaller than 300 nm. These systems were infiltrated
with monomers, which were crosslinked in the voids, or
preformed polymers. From this periodic composite structure, the silica opal was etched out and so-called inverse
polymer opals were formed. In this approach polymers such
as ferroelectric vinylidene fluoride trifluoroethylene copolymers [241], poly(3-alkylthiophene) [242], or bisphenol
A-epichlorohydrin copolymer epoxy resin were used [243].
Furthermore, monomers can also be polymerized in the
voids, for example ( p-xylenebis(tetrahydrothiophenium
chloride)), was polymerized in situ [244].
8. Applications
The possible applications of the described materials are
manifold and the future of these materials appears bright.
Especially, the tremendous possibilities of different combinations in nanocomposites between inorganic and organic
species, allow properties which cannot be obtained by
traditional composite materials. In this review only a limited
amount of applications can be exemplary introduced. The
examples follow the specific properties of the
nanocomposites.
Optical transparency. Although many of the features of
inorganic and organic polymeric moieties that are important
for optical issues such as the refractive index are very
different, the resulting material can often be prepared to be
optically transparent. This is based on the small length scale
over which phase separation may exist.
In order to implement optoelectronic or photonic
properties into devices, the materials have to fulfill high
optical quality demands and have to be stable over a long
period. Furthermore, the control of the refractive index as
well as the thickness and, therefore, the processibility of the
materials are important. Due to its low optical losses (high
optical quality), silica glass and composites made from it
seem to be very useful for these devices [245,246]. For
example, photoconducting composites were prepared by the
incorporation of cadmium sulfide particles in a polyvinylcarbazole matrix. The resulting materials allowed the tuning
of the band-gap of the sensitizing nanocrystals so that their
spectral response was adjusted to suit a particular wavelength of operation [247,248].
The already mentioned low optical loss of silica-based
composite materials, the ability to tune light scattering, and
depending on the composition of the low reflectivity, makes
such hybrid materials possible candidates as glues between
waveguide optical fiber interfaces. Therefore, they have
potential applications in optical interconnection devices
used in telecommunication networks. However, the problem
in such cases is the volume shrinkage. New composite
inorganic organic materials based on a silica and a
crosslinked polymer phase resulted in low volume shrinkage
during network formation [249].
Mechanical and thermal properties. The enhancement of
mechanical and thermal properties of polymers by the
inclusion of inorganic moieties, especially in the form of
nanocomposites, offers the possibility for these materials to
substitute classical compounds based on metals or on
traditional composites in the transportation industry. This is
especially interesting due to environmental issues and the
demand for lightweight materials resulting in a better fuel
economy [250].
Scratch-resistance or barrier property inorganic organic
coatings were developed by a polymer/sol gel approach
[37,251]. For example, UV curable systems were obtained
by the cocondensation of 3-(N-styrylmethyl-2-aminoethylamino)-propyltrimethoxysilane hydrochloride and varying
amounts of TMOS using 1-hydroxycyclohexylphenylketone
as photoinitiator (Fig. 4). Thermally curable compositions
consisted of TMOS, GLYMO, 3-aminopropyltriethoxysilane, aluminum-sec-butoxide, and zirconium-n-propoxide.
A study of these systems revealed that the oxygen
permeability decreased with increasing density of the
inorganic moiety as well as with the organic network,
which was varied through the ratios of the precursors [251].
Alteration of optical properties. Third order non-linear
optical (NLO) materials were obtained by composites based
on sol gel processed inorganic oxide/conjugated polymers.
Organic polymers with p-electron conjugation are an
important class of potentially useful NLO-materials due to
their large non-resonant third-order non-linearity with fast
response time. However, pure PPV films exhibit relatively
high optical losses, while silica has a low optical loss, its
non-linear susceptibility is very low. Therefore, a combination of both systems leads to new materials with superior
NLO properties [252].
Nanocomposite-based devices for electronic and optoelectronic applications include light-emitting diodes, photodiodes, solar cells, gas sensors and field effect transistors.
While most of these devices can also be produced as fully
organic polymer-based systems, the composites with
inorganic moieties have important advantages such as the
improvement of long-term stability, the improvement of
105
Fig. 4. Composition of (a) UV curable and (b) thermally curable inorganicorganic hybrids for application as oxygen barrier coatings.
electronic properties by doping with functionalized

particles, and the tailoring of the band gap by changing
the size of the particles [253].
Switchable inorganic organic hybrid materials have
been formed by the incorporation of switchable species into
a polymer/sol gel mixture. For example, azobenzenemodified poly(2MOx) was synthesized and incorporated in
a silica sol gel network. The photochemical induced
trans cis isomerization of the azobenzene chromophores
in the polymer hybrid was confirmed by absorption
spectra [254]. A reverse photochromism was also observed
in a spiropyran-modified poly(N,N-dimethylacrylamide)
embedded in a silica matrix. Based on the solvatochromic
behavior of the chromophore, which is different in a pure
silica matrix than in a polymer matrix, it was concluded that
the spyropyran is surrounded solely by the organic polymer
(Scheme 15) [255].
Chemical sensors. A composite from poly(Py) derivatives and tin dioxide gave reversible changes in electrical
resistance at room temperature when exposed to a variety of
different organic vapors, such as esters, alcohols, and
ketones. The sensitivity of this device was in the range of
existing sensors based on ceramic materials or pure polymer
films [256].
Self-organization. Colloidal crystals, which can be used
in different optical applications, were produced by the
modification of monodisperse, charged, nanometer-sized
colloidal silica particles with MEMO in methyl acrylate.
These dispersions can be photopolymerized and the
resulting composites show Bragg diffraction which is an

indication of 3D ordering in the resulting material. The
diffraction wavelength is tuned by varying the d-spacing of
the crystal lattice and the Bragg angle [176,257,258].
Conducting properties. Composite electrolyte materials
for applications such as solid-state lithium batteries or
supercapacitors have been produced using organic inorganic polymeric systems formed by the mixture of organic
polymers and inorganic moieties prepared by the sol gel
techniques. In these systems at least one of the network
forming species should contain components that allow an
interaction to the conducting ions. This is often realized
using organic polymers which allow an interaction with the
ions such as poly(EO) [259 261]. Another method towards
these materials is the cocondensation of alkyl-sulfone
functionalized alkoxysilanes with reactive polymerizable
alkoxysilanes such as MEMO and GLYMO and UV, or
thermal induced polymerization of the functional groups.
The resulting materials were optically transparent, water
stable, proton conducting membranes in which the proton
conducting ability was dependent on the content of SO3H
groups and coordinated water [262,263]. Proton conducting
composites were also obtained by the formation of
IPNs from silicon alkoxide end-capped poly(EO),
phenyltriethoxysilane using monododecylphosphate or
phosphotungstic acid to induce the proton conductivity
[264]. The application of hybrid composites is interesting
for these systems due to their membrane stability at high
temperatures compared to pure organic systems.
106
Scheme 15.
The combination of conducting polymers with inorganic

species is another example for nanocomposites with a
potentially important application. A variety of combinations
have already been tested and especially poly(An) and
poly(Py) show an interesting potential in combination with
iron oxides, barium titanate, platinum, and tungsten oxide
for magnetical, energy storage, catalytic, and electrochromic devices, respectively [265].
9. Summary
The incorporation of nanoscale inorganic species in
organic polymers offers the possibility of the formation
of a plethora of novel materials with a high potential for
new application. For optimal control of the properties of
these new materials, it is highly important to tailor the
formation process from the point of view of the final
product. For example, the formation of highly optical
transparent material requires another process other than
that of a system with good thermal and mechanical
properties. At the present time, this very interdisciplinary scientific area is open for new ideas from all
disciplines and therefore a promising future can be
foreseen.
Acknowledgements
The author thanks Ulrich Schubert and Nicola Husing for
fruitful discussions, Susan Thompson for technical assistance, and the Fonds fur wissenschaftliche Forschung,
Vienna, for financial support of his work.
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Concepts For The Incorporation of Inorganic Building Blocks Into Organic Polymers On A Nanoscale

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Prog. Polym. Sci.

Concepts for the incorporation of inorganic building blocks

* Tel.: 43-1-58801-15321; fax: 43-1-58801-15399.

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

Additionally, the properties of the composite materials

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

inorganic component must fail due to the limited thermal

different morphologies of the materials are the water to

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

have specific interactions with compounds created in the

high degree of homogeneity and optical transparency.

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

influence on the resulting material. In a hybrid material

2.2. Polymerization in sol gel networks

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

studies on a HEA/TEOS system revealed that there is a

groups in the SiO2 network using trialkoxysilanes. Even pp

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

is able to react in an organic polymerization, for example, a

3. Incorporation of metals and metal complexes in

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

plasma polymers, and (v) mechanochemical synthesis [81].

single chains or crosslinking by bridging coordination sites.

3.3. Metal-centered polymers

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

4. Intercalation in 2D layered materials

are more interested are referred to more detailed reviews and

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

based on special properties, e.g. the higher degree of

Intercalation of monomers followed by in situ

(ii) Direct intercalation of polymer chains from solution.

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

cations. These cations lower the surface energy of the

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

nearly any kind of inorganic material with any kind of

5. Intercalation in 3D frameworks: zeolites, molecular

materials is their ability to discriminate between shapes and

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

[150]. To obtain high optical transparency the refractive

types of conducting polymers have been prepared in the host

6. Incorporation of inorganic particles and clusters

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

6.1. Incorporation of unmodified particles

[162 164]. The formation of an initial hydrophobic layer

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

6.3. In situ growth of inorganic particles in a polymer matrix

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

prepared by well-established techniques. However, for a

as acrylate, vinylpyridine, vinylimidazole, acrylonitrile, etc.

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

acetonitrile with ethyl methacrylate in different ratios (1:10

cluster crosslinked poly(MMA) was insoluble in common

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

soluble in organic solvents, e.g. THF, toluene, hexane and

the pending linear polymeric structure allows for an easier

Free radical polymerization

Free radical polymerization

Epoxy resin formation

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

388 8C. Styrylethyl-substituted systems were homo- and

cyclopentyl to cyclohexyl also affects the Tg in such a

G. Kickelbick / Prog. Polym. Sci. 28 (2003) 83114

attached to the surface by a series of modifications. The